U.S. patent application number 13/692799 was filed with the patent office on 2014-06-05 for latex carrier coating and methods for making the same.
This patent application is currently assigned to XEROX CORPORATION. The applicant listed for this patent is XEROX CORPORATION. Invention is credited to VALERIE FARRUGIA, Paul J. Gerroir, Michael S. Hawkins, Karen Moffat, Richard P. Veregin.
Application Number | 20140154622 13/692799 |
Document ID | / |
Family ID | 50825770 |
Filed Date | 2014-06-05 |
United States Patent
Application |
20140154622 |
Kind Code |
A1 |
FARRUGIA; VALERIE ; et
al. |
June 5, 2014 |
LATEX CARRIER COATING AND METHODS FOR MAKING THE SAME
Abstract
A carrier coating comprising a metal core and a polymeric
coating that may be used to form toner. The carrier coating,
through how it is made, exhibits improved coating abilities that
may be used to completely coat carrier particles, and thus provide
excellent aging performance.
Inventors: |
FARRUGIA; VALERIE;
(Oakville, CA) ; Gerroir; Paul J.; (Oakvill,
CA) ; Hawkins; Michael S.; (Cambridge, CA) ;
Veregin; Richard P.; (Mississauga, CA) ; Moffat;
Karen; (Brantford, CA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
XEROX CORPORATION |
Norwalk |
CT |
US |
|
|
Assignee: |
XEROX CORPORATION
Norwalk
CT
|
Family ID: |
50825770 |
Appl. No.: |
13/692799 |
Filed: |
December 3, 2012 |
Current U.S.
Class: |
430/109.3 ;
252/500; 430/110.2 |
Current CPC
Class: |
G03G 9/1133 20130101;
G03G 9/107 20130101; G03G 9/1131 20130101; G03G 9/1139
20130101 |
Class at
Publication: |
430/109.3 ;
252/500; 430/110.2 |
International
Class: |
G03G 9/113 20060101
G03G009/113 |
Claims
1. A latex composition for coating carrier cores comprising: a
first monomer; a second monomer; and a conductive filler, wherein a
total residual monomer is less than 0.5 percent by weight of the
total weight of the latex composition.
2. The latex composition of claim 1, wherein the first monomer is
cyclohexylmethacrylate.
3. The latex composition of claim 1, wherein the second monomer is
dimethylaminoethylmethacrylate.
4. The latex composition of claim 1 being generated from a
semi-continuous emulsion polymerization of the first and second
monomers.
5. The latex composition of claim 1 further comprising one or more
change enhancing additives.
6. A carrier particle comprising: a carrier core; and a carrier
coating disposed over the carrier core, wherein the carrier coating
comprises a latex composition comprising a first monomer being an
aliphatic cycloacrylate, a second monomer being a
dialkylmethacrylate, and a conductive filler, wherein a total
residual monomer of the first and second monomer is less than 0.5
percent by weight of the total weight of the latex composition.
7. The carrier particle of claim 6, wherein the carrier core
comprises a material selected from the group consisting of granular
zircon, granular silicon, glass, steel, nickel, ferrites,
magnetites, iron ferrites, silicon dioxide, and mixtures
thereof.
8. The carrier particle of claim 6, wherein the carrier core has a
diameter in the range of from about 30 micrometers to about 400
micrometers.
9. The carrier particle of claim 6, wherein the carrier coating
covers from about 50 percent to about 100 percent of the surface
area of the carrier core.
10. The carrier particle of claim 9, wherein the carrier coating
covers from about 80 percent to about 100 percent of the surface
area of the carrier core.
11. A developer for developing electrostatic latent images,
comprising: a toner comprising at least a binder resin; and carrier
particles of claim 6.
12. The developer of claim 11, wherein the binder resin is a vinyl
polymer resin.
13. The developer of claim 11, wherein the toner is an emulsion
aggregation toner.
14. The developer of claim 11, wherein the toner further comprises
one or more amorphous resins.
15. A latex composition for coating carrier cores comprising:
cyclohexylmethacrylate; dimethylaminoethylmethacrylate; and a
conductive filler, wherein the amount of cyclohexylmethacrylate and
dimethylaminoethylmethacrylate is less than 0.5 percent by weight
of the total weight of the latex composition.
16. (canceled)
17. (canceled)
18. (canceled)
19. (canceled)
20. (canceled)
21. The carrier particle of claim 6, wherein the latex composition
further comprises one or more charge enhancing additives.
Description
BACKGROUND
[0001] Herein disclosed are embodiments that relate generally to
carrier particles comprising a metal core and a polymeric coating
that may be used to form toner. More particularly, the embodiments
relate to the carrier coating for xerographic carriers which
provides complete coverage of the metal core and thus excellent
aging performance.
[0002] The electrostatographic process, and particularly the
xerographic process, involves the formation of an electrostatic
latent image on a photoreceptor, followed by development of the
image with a developer, and subsequent transfer of the image to a
suitable substrate. Numerous different types of xerographic imaging
processes are known wherein, for example, insulative developer
particles or conductive developer particles are selected depending
on the development systems used. It is of great importance that
such developer compositions are associated with the appropriate
triboelectric charging values as it is these values that enable
continued formation of developed images of high quality and
excellent resolution. In two component developer compositions,
carrier particles are used in charging the toner particles.
[0003] The resulting toners can be selected for known
electrophotographic imaging and printing processes, including
digital color processes, and are especially useful for imaging
processes, specifically xerographic processes, which usually
require high toner transfer efficiency such as those having a
compact machine design without a cleaner or those that are designed
to provide high quality colored images with excellent image
resolution and signal-to-noise ratio and image uniformity, and for
imaging systems wherein excellent glossy images are generated.
[0004] Carrier particles in part consist of a roughly spherical
core, often referred to as the "carrier core," which may be made
from a variety of materials. The core is typically coated with a
resin. This resin may be made from a polymer or copolymer. The
resin may have conductive material or charge enhancing additives
incorporated into it to provide the carrier particles with more
desirable and consistent triboelectric properties. The resin may be
in the form of a powder, which may be used to coat the carrier
particle. Often the powder or resin is referred to as the "carrier
coating" or "coating."
[0005] Various coated carrier particles for use in
electrostatographic developers for the development of electrostatic
latent images are described in patents. For example, U.S. Pat. No.
3,590,000 discloses carrier particles that may consist of various
cores, including steel, with a coating thereover of fluoro-polymers
and ter-polymers of styrene, methacrylate, and silane
compounds.
[0006] One common way of obtaining carrier coating is in the form
of powder via emulsion polymerization. This particular method of
polymerization has been described in patents, for example, U.S.
Pat. Nos. 6,042,981 and 5,290,654, incorporated herein by
reference. Emulsion polymerization, yielding excellent control over
particle size and size distribution, is most typically accomplished
by the continuous or semi-continuous addition of monomer to a
suitable reaction vessel containing water. The reaction vessel is
provided with stirring means, and also optionally, nitrogen
atmosphere and thermostatic control. The polymerization is affected
by heating to, for example, between about 40.degree. C. and about
85.degree. C., and with the addition of an appropriate initiator
compound, such as ammonium persulfate. The polymer or copolymer
powders are isolated by freeze drying in vacuo or by conventional
spray drying the residue-free latex. The resulting polymer particle
diameter size is, for example, from about 0.1 to about 12.0 microns
in volume average diameter, but exhibits excellent friability when
blended with a bare carrier core.
[0007] To meet the demands of toner performance, such as aging
performance, complete coating of the carrier surface is required.
It is desirable to coat the carrier as completely as possible to
prevent increase in conductivity in aging. The conventional
approach is to increase the coating weight, which is undesirable as
it increases manufacturing cost and complicates the manufacturing
process. Moreover, adding additional coating tends to make
particles stick together, which then leads to large surface coating
defects when the carrier particles are separated in the screening
step. Further, the higher the coating weight the more likely poor
flow of the carrier will occur in the kiln, reducing throughput
(higher throughput on the kilns has been critical to cost
reductions), and increasing the likelihood of coating resin
agglomerates which are known to cause print defects. Thus, there is
a need for a carrier coating that provides complete carrier
coverage.
BRIEF SUMMARY
[0008] Embodiments include a carrier coating for xerographic
carriers which provides complete coverage of the metal core and
thus excellent aging performance and methods for making the
same.
[0009] In embodiments, there is provided a latex composition for
coating carrier cores comprising: a first monomer; a second
monomer; and a conductive filler, wherein the residual monomer of
the first monomer and second monomer is less than 0.5 percent by
weight of the total weight of the latex composition.
[0010] In further embodiments, there is provided a carrier particle
comprising: a carrier core; and a carrier coating disposed over the
carrier core, wherein the carrier coating comprises a first
monomer, a second monomer, and a conductive filler, wherein the
total residual monomer is less than 0.5 percent by weight of the
total weight of the latex composition. In such embodiments, there
is also provided a developer for developing electrostatic latent
images, comprising: a toner comprising at least a binder resin; and
the carrier particles described above.
[0011] In yet further embodiments, there is provided a latex
composition for coating carrier cores comprising:
cyclohexylmethacrylate; dimethylaminoethylmethacrylate; and a
conductive filler, wherein the amount of cyclohexylmethacrylate and
dimethylaminoethylmethacrylate is less than 0.5 percent by weight
of the total weight of the latex composition.
[0012] In other embodiments, there is provided a process for making
a latex composition for coating carrier cores comprising: mixing
one or more surfactants in de-ionized water to form a surfactant
solution; mixing a first monomer, a second monomer and one or more
surfactants in de-ionized water to form a monomer solution;
combining the specific amounts of the monomer solution with the
surfactant solution to form seed particles; and subjecting the
combined surfactant solution and monomer solution to
semi-continuous emulsion polymerization.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] FIG. 1 is a graph illustrating the correlation between the
percentage of residual CHMA and exposed carrier core;
[0014] FIG. 2 are Scanning Electron Microscopy (SEM) images
illustrating the surface of a typical carrier prepared with each of
four latex samples prepared according to the present embodiments
(A=Example 1; B=Example 2; C=Example 3; and D=Example 4);
[0015] FIG. 3 is a graph illustrating charge of toners prepared
according to the present embodiments in both A-zone and J-zone;
[0016] FIG. 4 is a graph illustrating charge of additional toners
prepared according to the present embodiments in both A-zone and
J-zone; and
[0017] FIG. 5 is a graph illustrating relative humidity ratios for
toners prepared according to the present embodiments.
DETAILED DESCRIPTION
[0018] In the following description, it is understood that other
embodiments may be used and structural and operational changes may
be made without departing from the scope of the present
embodiments.
[0019] The present embodiments relate to coating composition for
carrier particles that, in embodiments, provide improved carrier
surface coating than conventional carrier coatings. In particular,
a polymer latex is used as a carrier coating and the method of
making the latex imparts the latex with improved coating
coverage.
[0020] In general embodiments, a latex resin may be composed of a
first and a second monomer composition. Any suitable monomer or
mixture of monomers may be selected to prepare the first monomer
composition and the second monomer composition. The selection of
monomer or mixture of monomers for the first monomer composition is
independent of that for the second monomer composition and vise
versa. In embodiments, the first monomer composition and the second
monomer composition can be the same.
[0021] Exemplary monomers for the first and/or the second monomer
compositions include, but are not limited to styrene, alkyl
acrylate, such as, methyl acrylate, ethyl acrylate, butyl arylate,
isobutyl acrylate, dodecyl acrylate, n-octyl acrylate,
2-chloroethyl acrylate; .beta.-carboxy ethyl acrylate (.beta.-CEA),
phenyl acrylate, methyl alphachloroacrylate, methyl methacrylate,
ethyl methacrylate and butyl methacrylate: butadiene; isoprene;
methacrylonitrile; acrylonitrile; vinyl ethers, such as, vinyl
methyl ether, vinyl isobutyl ether, vinyl ethyl ether and the like;
vinyl esters, such as, vinyl acetate, vinyl propionate, vinyl
benzoate and vinyl butyrate; vinyl ketones, such as, vinyl methyl
ketone, vinyl hexyl ketone and methyl isopropenyl ketone;
vinylidene halides, such as, vinylidene chloride and vinylidene
chlorofluoride; N-vinyl indole; N-vinyl pyrrolidone; methacrylate;
acrylic acid; methacrylic acid; acrylamide; methacrylamide;
vinylpyridine; vinylpyrrolidone; vinyl-N-methylpyridinium chloride;
vinyl naphthalene; p-chlorostyrene; vinyl chloride; vinyl bromide;
vinyl fluoride; ethylene; propylene; butylenes; isobutylene; and
the like, and mixtures thereof. In case a mixture of monomers is
used, typically the latex polymer will be a copolymer.
[0022] In some embodiments, the first monomer composition and the
second monomer composition may independently of each other comprise
two or three or more different monomers. The latex polymer
therefore can comprise a copolymer. Illustrative examples of such a
latex copolymer includes poly(styrene-n-butyl acrylate-.beta.-CEA),
poly(styrene-alkyl acrylate), poly(styrene-1,3-diene),
poly(styrene-alkyl methacrylate), poly(alkyl methacrylate-alkyl
acrylate), poly(alkyl methacrylate-aryl acrylate), poly(aryl
methacrylate-alkyl acrylate), poly(alkyl methacrylate),
poly(styrene-alkyl acrylate-acrylonitrile),
poly(styrene-1,3-diene-acrylonitrile), poly(alkyl
acrylate-acrylonitrile), poly(styrene-butadiene),
poly(methylstyrene-butadiene), poly(methyl methacrylate-butadiene),
poly(ethyl methacrylate-butadiene), poly(propyl
methacrylate-butadiene), poly(butyl methacrylate-butadiene),
poly(methyl acrylate-butadiene), poly(ethyl acrylate-butadiene),
poly(propyl acrylate-butadiene), poly(butyl acrylate-butadiene),
poly(styrene-isoprene), poly(methylstyrene-isoprene), poly(methyl
methacrylate-isoprene), poly(ethyl methacrylate-isoprene),
poly(propyl methacrylate-isoprene), poly(butyl
methacrylate-isoprene), poly(methyl acrylate-isoprene), poly(ethyl
acrylate-isoprene), poly(propyl acrylate-isoprene), poly(butyl
acrylate-isoprene); poly(styrene-propyl acrylate),
poly(styrene-butyl acrylate),
poly(styrene-butadiene-acrylonitrile), poly(styrene-butyl
acrylate-acrylononitrile), and the like.
[0023] In embodiments, the first monomer composition and the second
monomer composition may be substantially water insoluble, such as,
hydrophobic, and may be dispersed in an aqueous phase with adequate
stirring when added to a reaction vessel.
[0024] The weight ratio between the first monomer composition and
the second monomer composition may be in the range of from about
0.1:99.9 to about 50:50, including from about 0,5:99.5 to about
25:75, from about 1:99 to about 10:90.
[0025] In specific present embodiments, the latex is generated from
the semi-continuous emulsion polymerization of
cyclohexylmethacrylate (CHMA) and dimethylaminoethylmethacrylate
(DMAEMA) monomers. As disclosed in U.S. Patent Publication No.
2011/0070538, the combination of cyclic aliphatic acrylate and
amino charge control monomer exhibits higher performance in
combination with polyester toners when compared to polymethyl
methacrylate (PMMA) latexes used previously for styrene/acrylate
toners. However, it was discovered that such latexes were not
stable with time and had unacceptably poor shelf life. The addition
of increase surfactant was found to somewhat address the shelf life
issue, as disclosed in U.S. patent appln. Ser. No. 13/295,067 filed
Nov. 12, 2011 to Vanbesien et al. The present embodiments, have
been able to achieve far superior stability and shelf life time
through a new process of preparing the latex for the CHMA/DMAEMA
carrier coating.
[0026] In particular, it was discovered that the percentage of
residual CHMA in the latex prepared with semi-continuous emulsion
polymerization process influences the coverage of the metal core.
In embodiments, the residual monomer of the two or more monomers
used to make the latex is to be less than 0.5% for all monomers
reacted in the emulsion polymerization process. In such a case, it
was found that better carrier coating coverage is achieved by
changing the emulsification conditions to lower the residual
CHMA.
[0027] It is believed that the residual monomer plasticizes the
latex and can cause the latex coating to become tacky and
aggregated such that it does not spread smoothly over the carrier
core. The residual monomer is generally the leftover monomer that
has not been reacted into the polymer chain. A factor that
influences the amount of residual monomer is the amount of seed
used initially for the polymerization. It was discovered by the
present inventors that the amount of exposed carrier core decreases
as the amount of residual CHMA reduces. Semi-continuous emulsion
polymerization is used in which aqueous phase-containing water and
surfactant is partitioned allowing for additional surfactant to be
added later in the process after seed particles have been
generated. As used herein, "seed particles" is defined as the
following. In the seeded polymerization process, either an external
or an in-situ seed is used. The external seed is generally a very
small particle size latex made by the batch polymerization process.
This latex can be stored and used as needed as a seed to polymerize
and grow larger particle size latex products. The in-situ seed
preparation process is the first stage of a continuous
polymerization process where water, emulsifiers, chelates and a
small portion of the monomer, alone or with a comonomer, are
polymerized to form the desired number of seed polymer particles.
The amount of monomer used for seed determines the number and size
of seed particles formed and the particle growth of the final latex
product. The seed, once formed, is followed by a second stage of
successive additions of the remaining monomers to be used to form
the final latex product. Seed monomers plus additional monomers
total 100 parts by weight.
[0028] Thus, better coating coverage is achieved by changing the
emulsification conditions to lower the residual CHMA. The improved
coverage also results in the more stable aging performance for
carrier conductivity. The charge and relative humidity sensitivity
for the present toners are also improved. Moreover, because
increased coating weight is not necessary, cost reductions are also
observed.
[0029] In embodiments, the amount of residual monomer is less than
0.5 percent by weight of the total weight of the latex composition.
In other embodiments, the amount of residual monomer is from about
0.05 to about 0.45 percent by weight of the total weight of the
latex composition. In further embodiments, the amount of residual
monomer is from about 0.30 to about 0.35 percent by weight of the
total weight of the latex composition. The amount of residual
monomer is measured by Perkin-Elmer gas chromatography (GC).
[0030] In embodiments, the latexes are generated as follows. The
polymerization of these latexes occurs in the temperature range
from about 10.degree. C. to about 100.degree. C. The polymerization
of the latexes is accomplished by heating at an effective
temperature such as from about 20.degree. C. to about 90.degree.
C., in alternative embodiments, from about 45.degree. C. to
75.degree. C. For the polymerization, there are usually selected
known initiators, such as radical initiators capable of initiating
a free radical polymerization process. Examples of initiators
include water soluble initiators, such as ammonium persulfate,
sodium persulfate and potassium persulfate, and organic soluble
initiators including organic peroxides and azo compounds including
Vazo peroxides, such as VAZO 64.TM., 2-methyl 2-2'-azobis
propanenitrile, VAZO 88.TM., 2-2'-azobis isobutyramide dehydrate,
and combinations thereof. Other water-soluble initiators which may
be utilized include azoamidine compounds, for example 2,
2'-azobis(2-methyl-N-phenylpropionamidine) dihydrochloride,
2,2'-azobis[N-(4-chlorophenyl)-2-methylpropionamidine]di-hydrochloride,
2,2'-azobis[N-(4-hydroxyphenyl)-2-methyl-propionamidine]dihydrochloride,
2,2'-azobis[N-(4-amino-phenyl)-2-methylpropionamidine]tetrahydrochloride,
2,2'-azobis[2-methyl-N(phenylmethyl)propionamidine]dihydrochloride,
2,2'-azobis[2-methyl-N-2-propenylpropionamidine]dihydrochloride,
2,2'-azobis[N-(2-hydroxy-ethyl)-2-methylpropionamidine]dihydrochloride,
2,2'-azobis[2(5-methyl-2-imidazolin-2-yl)propane]dihydrochloride,
2,2'-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride,
2,2'-azobis[2-(4,5,6,7-tetrahydro-1H-1,3-diazepin-2-yl)propane]dihydrochl-
oride,
2,2'-azobis[2-(3,4,5,6-tetrahydropyrimidin-2-yl)propane]dihydrochlo-
ride,
2,2'-azobis[2-(5-hydroxy-3,4,5,6-tetrahydropyrimidin-2-yl)propane]di-
hydrochloride,
2,2'-azobis{2-[1-(2-hydroxyethyl)-2-imidazolin-2-yl]propane}dihydrochlori-
de, combinations thereof, and the like. Suitable initiators are
also described in U.S. Pat. No. 8,227,163, which is hereby
incorporated by reference in its entirety. Initiators can be added
in suitable amounts such as, for example, from about 0.1 to about 8
weight percent of the total weight of monomer to be polymerized,
and which amount is determined by the desired molecular weight of
the resin. In other embodiments, the initiator is added in an
amount of from about 0.2 to about 5 weight percent of the
monomers.
[0031] In the present embodiments, the polymerization is carried
out in partitioned steps to allow additional surfactant to be added
later in the process after seed particles have been generated. An
aqueous surfactant solution comprising a surfactant in de-ionized
water was mixed. Separately, a monomer solution of a first and
second monomers was mixed with a surfactant and de-ionized water.
In specific embodiments, the first and second monomers are CHMA and
DMAEMA. Specific amounts of the monomer solution were combined with
the aqueous surfactant solution in a Buchi reactor (commercially
available from Buchi AG Uster (Uster, Switzerland)) as seed. In
embodiments, the amounts of monomer solution added to the aqueous
surfactant solution to form seed particles is from about 0.1 to
about 10 percent, or from about 1 to about 9 percent, or from about
1 to about 8 percent. Surfactants may be present in amounts of, for
example, or from about 0.01 to about 15 percent, or from about 0.1
to about 5 percent by weight of the total weight of the aqueous
surfactant solution. Surfactants may be present in amounts of, for
example, or from about 0.05 to about 15 percent, or from about 0,5
to about 10 percent by weight of the total weight of the monomer
solution.
[0032] The surfactants may include, for example, nonionic
surfactants such as dialkylphenoxypoly(ethyleneoxy) ethanol,
available from Rhone-Poulenac as IGEPAL CA-210, IGEPAL CA-520,
IGEPAL CA-720., IGEPAL CO-890, IGEPAL CO-720.TM., IGEPAL CO-290.,
IGEPAL CA-210. An effective concentration of the nonionic
surfactant is in embodiments, for example, from about 0.1 to about
5 percent by weight, and preferably from about 0.4 to about 1
percent by weight of monomer, or monomers selected to prepare the
copolymer resin of the emulsion. Examples of nonionic surfactants
include, but are not limited to, alcohols, acids and ethers, for
example, polyvinyl alcohol, polyacrylic acid, methalose, methyl
cellulose, ethyl cellulose, propyl cellulose, hydroxylethyl
cellulose, carboxy methyl cellulose, polyoxyethylene cetyl ether,
polyoxyethylene lauryl ether, polyoxyethylene octyl ether,
polyoxyethylene octylphenyl ether, polyoxyethylene oleyl ether,
polyoxyethylene sorbitan monolaurate, polyoxyethylene stearyl
ether, polyoxyethylene nonylphenyl ether, dialkylphenoxy
poly(ethyleneoxy)ethanol, combinations thereof, and the like. In
embodiments commercially available surfactants from Rhone-Poulenc
such as IGEPAL CA210.TM., IGEPAL CA-520.TM., IGEPAL CA720.TM.,
IGEPAL C0890.TM., IGEPAL CO720.TM., IGEPAL CO290.TM., IGEPAL
CA-210.TM., ANTAROX 890.TM. and ANTAROX 897.TM. can be
utilized.
[0033] Examples of ionic surfactants include sodium dodecylsulfate
(SDS), sodium dodecylbenzene sulfonate, sodium dodecylnaphthalene
sulfate, dialkyl benzenealkyl, sulfates and sulfonates, available
from Aldrich, NEOGEN R.TM., NEOGEN SC.TM. obtained from Kao, and
the like. An effective concentration of the anionic surfactant
generally employed is, for example, from about 0.1 to about 5
percent by weight, and preferably from about 0.4 to about 1 percent
by weight of monomers or monomer used to prepare the copolymer
emulsion. Other suitable anionic surfactants include, in
embodiments, DOWFAX.TM. 2A1, an alkyldiphenyloxide disulfonate from
The Dow Chemical Company, and/or TAYCA POWER BN2060 from Tayca
Corporation (Japan), which are branched sodium dodecyl benzene
sulfonates. Combinations of these surfactants and any of the
foregoing anionic surfactants may be utilized in embodiments.
[0034] Examples of specific cationic surfactants include, but are
not limited to, ammoniums, for example, alkylbenzyl dimethyl
ammonium chloride, dialkyl benzenealkyl ammonium chloride, lauryl
trimethyl ammonium chloride, alkylbenzyl methyl ammonium chloride,
alkyl benzyl dimethyl ammonium bromide, benzalkonium chloride, C12,
C15, C17 trimethyl ammonium bromides, combinations thereof, and the
like. Other cationic surfactants include cetyl pyridinium bromide,
halide salts of quaternized polyoxyethylalkylamines, dodecylbenzyl
triethyl ammonium chloride, MIRAPOL and ALKAQUAT available from
Alkaril Chemical Company, SANISOL (benzalkonium chloride),
available from Kao Chemicals, combinations thereof, and the like.
In embodiments a suitable cationic surfactant includes SANISOL B-50
available from Kao Corp., which is primarily a benzyl dimethyl
alkonium chloride, and the like.
[0035] The monomer or monomer mixture is gradually mixed into an
aqueous solution of surfactant preferably while maintaining
continuous mixing.
[0036] As described in U.S. Pat. No. 8,227,163, which is hereby
incorporated by reference in its entirety, in forming the
emulsions, the starting materials, surfactant, optional solvent,
and optional initiator may be combined utilizing any means within
the purview of those skilled in the art. In embodiments, the
reaction mixture may be mixed at a rate of, for example, about 50
to about 800 revolutions per minute for from about 1 minute to
about 72 hours using any mechanical mixing apparatus known in the
art. In further embodiments the mixing is performed at a rate of
about 300-600 revolutions per minute for about 4 to about 24 hours
(although times outside these ranges may be utilized), while
keeping the temperature at from about 10.degree. C. to about
100.degree. C., in embodiments from about 20.degree. C. to about
90.degree. C., in other embodiments from about 45.degree. C. to
about 75.degree. C., although temperatures outside these ranges may
be utilized.
[0037] Those skilled in the art will recognize that optimization of
reaction conditions, temperature, and initiator loading can be
varied to generate vinyl polymers of various molecular weights, and
that structurally related starting materials may be polymerized
using comparable techniques. The recovery of the polymer particles
from the emulsion polymerization can be accomplished by processes
known in the art. For example, the emulsion of polymer particles
can first be filtered by any suitable material. In another
embodiment, a cheese cloth is used. The polymer particles can then
be washed, but in a preferred embodiment, the polymer particles are
not washed, thus allowing some amount of the surfactant to remain
in association with the conductive polymer particles. Allowing some
amount of the surfactant to remain in association with the polymer
particles provides for better particle formation and better carrier
coating characteristics. Once the copolymer utilized as the coating
for a carrier has been formed, it may be recovered from the
emulsion by any technique within the purview of those skilled in
the art, including filtration, drying, centrifugation, spray
drying, combinations thereof, and the like. The surfactants'
interplay with the surface chemistry of the polymer particles
provides for these improved results. Finally, the polymer particles
are dried using, e.g., freeze drying, spray drying or vacuum
techniques well known in the art.
[0038] The polymer particles isolated from the process have an
initial size of, for example, from about 10 nanometers to 3
micrometers. Due to physical aggregates, some of the polymer
particles may initially have a size larger than 7 micrometer.
During the mixing process with the conductive filler and/or the
carrier cores, the physical aggregates of the polymer particles
will be broken up into smaller polymer particles. Preferably, the
polymer particles obtained by the process herein have a size of,
for example, from about 30 nanometers to about 1 micrometer, or
from about 50 nanometers to about 400 nanometers.
[0039] After the formation and recovery of the polymer particles,
at least one conductive filler is incorporated with the polymer
particles. The inclusion of conductive filler into carrier coating
composition is well known in the xerographic arts. Various types of
conductive filler may be incorporated into the present embodiments.
The conductive material described may be any suitable material
exhibiting conductivity, e.g., metal oxides like tin oxide, metals,
carbon black, and the like, whose size and surface area provide the
proper conductivity range. An exemplary carbon black is VULCAN XC72
(available from Cabot Corporation; Boston, Mass.), which has a
particle size of about 0.03 micrometers, and a surface area of
about 250 m.sup.2/g. The coating composition described herein
enables carriers to achieve a wide range of conductivity. Carriers
using the composition may exhibit conductivity of from about
10.sup.-7 to about 10.sup.-17 mho-cm.sup.-1 as measured, for
example, across a 0.1 inch magnetic brush at an applied potential
of 10 volts; and wherein the coating coverage encompasses from
about 10 percent to about 100 percent of the carrier core.
[0040] The conductive filler is incorporated into the polymer
particles using techniques well known in the art including the use
of various types of mixing and/or electrostatic attraction,
mechanical impaction, dry-blending, thermal fusion and others. The
composition may contain from about 0 percent to about 60 percent by
weight conductive filler, although in some embodiments the
micro-powder may contain only about 10 percent by weight of a
conductive filler.
[0041] In addition to incorporating conductive filler into carrier
coatings, it is often desirable to impart varying charge
characteristics to the carrier particle by incorporating charge
enhancing additives. If incorporated with the sub-micron sized
polymer particles, the charge enhancing additives may be
incorporated in a premixing process before or after the
incorporation of the conductive filler.
[0042] Typical charge enhancing additives include particulate amine
resins, such as melamine, and certain fluoro polymer powders such
as alkyl-amino acrylates and methacrylates, polyamides, and
fluorinated polymers, such as polyvinylidine fluoride (PVF.sub.2)
and poly(tetrafluoroethylene), and fluoroalkyl methacrylates such
as 2,2,2, trifluoroethyl methacrylate. Other charge enhancing
additives such as, for example, those illustrated in U.S. Pat. No.
5,928,830, incorporated by reference herein, including quaternary
ammonium salts, and more specifically, distearyl dimethyl ammonium
methyl sulfate (DDAMS), bis-1-(3,5-disubstituted-2-hydroxy
phenyl)axo-3-(mono-substituted)-2-naphthalenolato(2-) chromate(1-),
ammonium sodium and hydrogen (TRH), cetyl pyridinium chloride(CPC),
FANAL PINK.TM. D4830, and the like and others as specifically
illustrated therein may also be utilized in the present
embodiments.
[0043] The charge additives are added in various effective amounts,
such as from about 0.01 percent to about 15.0 percent by weight,
based on the sum of the weights of all polymer, conductive
additive, and charge additive components.
[0044] After the synthesis of the coating composition, including
the incorporation of conductive filler and optional charge
enhancing additives, the resin may be incorporated onto the surface
of the carrier. Various effective suitable processes can be
selected to apply a coating to the surface of the carrier
particles. Examples of typical processes for this purpose include
roll mixing, tumbling, milling, shaking, electrostatic powder cloud
spraying, fluidized bed, electrostatic disc processing, and an
electrostatic curtain. For example, see U.S. Pat. No. 6,042,981,
incorporated herein by reference.
[0045] Following incorporation of the coating composition onto the
surface of the carrier, heating may be initiated to permit flow of
the coating material over the surface of the carrier core. In a
preferred embodiment, the coating composition is fused to the
carrier core in either a rotary kiln or by passing through a heated
extruder apparatus.
[0046] In an embodiment, the conductive polymer particles are used
to coat carrier cores of any known type by any known method, which
carriers are then incorporated with any known toner to form a
developer for xerographic printing. Suitable carriers may be found
in, for example, U.S. Pat. Nos. 4,937,166 and 4,935,326,
incorporated herein by reference, and may include granular zircon,
granular silicon, glass, steel, nickel, ferrites, magnetites, iron
ferrites, silicon dioxide, and the like.
[0047] Carrier cores having a diameter in a range of, for example,
about 30 micrometers to about 400 micrometers may be used. In
further embodiments, the carriers are, for example, about 35
micrometers to about 100 micrometers.
[0048] Typically, the coating composition covers, for example,
about 10 percent to about 100 percent, or from about 50 percent to
about 100 percent, or from about 80 percent to about 100 percent of
the surface area of the carrier core using from about 0.1 percent
to about 20 percent coating weight, or from about 0.5 percent to
about 10 percent coating weight, or from about 0.7 percent to about
5 percent coating weight.
[0049] The coating composition of the present embodiments finds
particular utility in a variety of xerographic copiers and
printers, such as high speed xerographic color copiers, printers,
digital copiers and more specifically, wherein color copies with
excellent and substantially no background deposits are desirable in
copiers, printers, digital copiers, and the combination of
xerographic copiers and digital systems.
EXAMPLES
[0050] The examples set forth hereinbelow are being submitted to
illustrate embodiments of the present disclosure. These examples
are intended to be illustrative only and are not intended to limit
the scope of the present disclosure. Also, parts and percentages
are by weight unless otherwise indicated. Comparative examples and
data are also provided.
Example I
[0051] CHMA Latex with 1% DMAEMA--Process Using 2% Seed
[0052] A latex emulsion comprised of polymer particles generated
from the emulsion polymerization of cyclohexylmethacrylate (CHMA)
and dimethylaminoethylmethacrylate (DMAEMA) charge control monomer
with partitioned surfactant were prepared as follows:
[0053] A surfactant solution consisting of 1.11 mmoles (0.320 g)
sodium lauryl sulfate (anionic emulsifier) and 14.05 moles (253 g)
of de-ionized water was prepared by mixing at 800 RPM for 20
minutes in a 500 ml beaker. The aqueous surfactant solution was
then transferred into a 1 L Buchi reactor. The reactor was heated
up to 65.degree. C. at a controlled rate and continuously purged
with nitrogen while being stirred at 450 RPM.
[0054] In another 500 ml beaker 665.7 mmol (112 g) of CHMA was
weighed and 1% DMAEMA or 6.7 mmol (1.053 g) of DMAEMA was added to
the CHMA. To this monomer solution was added 2.43 mmol (0.701 g) of
sodium lauryl sulfate surfactant and 7.085 moles (128 g) of
de-ionized water. The contents in the beaker were stirred at 800
RPM to emulsify the monomer/aqueous surfactant solution.
[0055] Two percent by weight (4.84 g) of this monomer/aqueous
solution was added to the aqueous surfactant mixture in the Buchi
reactor as a seed. Separately prepared was a solution of 2.1 mmol
(0.479 g) ammonium persulfate initiator dissolved in 222 mmol (4.00
g) de-ionized water to form the initiator solution. The initiator
solution was then slowly charged into the reactor via pipette.
After 40 minutes of the Buchi stirring at 450 RPM and 65.degree.
C., the contents from the beaker containing the rest of the
monomer/aqueous solution were slowly metered in using a Fluid
Metering Inc. (FMI) metering pump at a rate of 0.9 g per minute.
Once all the monomer emulsion was charged into the Buchi, the
temperature was held at 65.degree. C. for an additional 3 hours to
complete the reaction. Full cooling was applied to the reactor to
bring the temperature to below 35.degree. C. A liquid sample was
taken to measure particle size on a Nanotrac Particle Size Analyzer
(Microtrac), zeta potential on a Zetasizer (Malvern) and evaluation
of residual monomer by a Perkin-Elmer gas chromatography (GC). The
rest of the product was dried to a powder form using a freeze-drier
apparatus.
Example 2
[0056] CHMA Latex with 1% DMAEMA--Process Using 4% Seed
[0057] Procedure was identical to Example 1 except that four
percent by weight (9.67 g) of this monomer/aqueous solution was
added to the aqueous surfactant mixture in the Buchi reactor as a
seed.
Example 3
[0058] CHMA Latex with 1% DMAEMA--Process Using 6% Seed
[0059] Procedure was identical to Example 1 except that six percent
by weight (14.51 g) of this monomer/aqueous solution was added to
the aqueous surfactant mixture in the Buchi reactor as a seed.
Example 4
[0060] CHMA Latex with 1% DMAEMA--Process Using 8% Seed
[0061] Procedure was identical to Example 1 except that eight
percent by weight (19.34 g) of this monomer/aqueous solution was
added to the aqueous surfactant mixture in the Buchi reactor as a
seed.
[0062] Evaluation of Residual Monomer
[0063] Residual monomer data was calculated for emulsion
polymerization experiments by gas chromatography (GC) using a
Perkin-Elmer XL Autosystem GC equipped with a flame ionization
detector and Supelcowax 10 column (15 m.times.0.53 mm ID; 0.5 .mu.m
film). The signal produced by the detector is unique for each
monomer and must be compared to a known sample for identification
and quantification. Standards (CHMA, DMAEMA) were prepared in
tetrahydrofuran (THF) in a concentration which fell in the linear
range of the detector response. Samples were weighed and dissolved
in a compatible organic solvent by shaking the vial for about 30
minutes in order to extract the volatile components. Standards and
samples were then transferred to GC vials. The latex, containing
approximately 20% solids in water, was diluted quantitatively 1 to
10 with solvent (THF), and 50 .mu.l of solvent portion containing
residual monomer was injected into the instrument by means of a
hypodermic syringe. To obtain vaporization of the volatile
components, the temperature of the injector block was increased.
The resulting gas chromatogram represents the residual CHMA present
in the latex.
Example 5
[0064] Preparation of Carrier and Developer
[0065] In a 250 ml PE bottle was added 120 grams of a 35 micron
ferrite core (carrier core) and 1.44 grams of the carrier polymer
latex. The bottle was then sealed and loaded into a J-zone Turbula
mixer (commercially available from Willy A. Bachofen AG
Maschinenfabrik (Basel, Switzerland)). The Turbula mixer was run
for 45 minutes to disperse powders onto carrier core particles.
Next the Haake mixer (commercially available from Thermo Electron
(USA)) was setup with the following conditions: set temp
200.degree. C. (all zones), 30 minute batch time, 30 RPM with high
shear rotors. After the Haake reaches temperature, the mixer
rotation was started and the blend was transferred from the Turbula
into the Haake mixer. After 30 minutes, the carrier was discharged
from mixer and sieved through a 45 um screen.
[0066] Microscopy and Determination of Coating Coverage
[0067] The carrier samples were examined using a Hitachi SU8000
scanning electron microscope. The following images were acquired in
such a way as to highlight areas of exposed core, which in the
micrographs appear brighter relative to the latex coating. Using
Image-Pro.RTM. Plus software (commercially available from Media
Cybernetics, Inc. (Rockville, Md.)) determinations were made from
these images of the percent exposed core. The data contained in
Table 1 and FIG. 1 shows a good correlation between the percentage
of residual CHMA and exposed core. The amount of residual DMAEMA
was negligible or not detected.
TABLE-US-00001 TABLE 1 % CHMA % Exposed Sample ID Residual Core
Example 1 - 2% seed 0.52 12.2 Example 2 - 4% seed 0.45 8.5 Example
3 - 6% seed 0.28 3.4 Example 4 - 8% seed 0.36 5.7
[0068] FIG. 2 are Scanning Electron Microscopy (SEM) images
illustrating the surface of a typical carrier prepared with each of
four latex samples for the four examples (A=Example 1; B=Example 2;
C=Example 3; and D=Example 4). The bright areas correspond to the
exposed core, the darker regions latex coating. It is expected that
better coating coverage will improve stability to aging
performance.
[0069] Charging Data
[0070] Toner charging results using these carriers were obtained by
preparing a developer at 5% toner concentration using a XEROX 700
toner, both parent and that blended with toner additives. Carrier
weight was 10 grams. After conditioning samples a minimum of 48
hours for J-zone (at about 21.1.degree. C. and 10% RH), and a
minimum 24 hours for A-zone (at about 28.degree. C./85% relative
humidity), the developers were charged in a Turbula mixer 10 mins
for parent developer and 60 minutes for the additive developer. The
toner charge was measured in the form of q/d, the charge to
diameter ratio. The q/d was measured using a charge spectrograph.
A-zone samples are measured with 100 V/cm and J-zone samples are
measured with 50 V/cm field, and are measured visually as the
midpoint of the toner charge distribution. The charge was reported
in millimeters of displacement from the zero line, corrected to 100
V/cm (2.times.the 50 V/cm values). The final mm displacement can be
converted to femtocoulombs/micron (fC/.mu.m) by multiplying by
0.092.
[0071] The toner charge per mass ratio (Q/M) was also determined by
the total blow-off charge method, measuring the charge on a faraday
cage containing the developer after removing the toner by blow-off
in a stream of air. The total charge collected in the cage is
divided by the mass of toner removed by the blow-off, by weighing
the cage before and after blow-off to give the Q/M ratio.
[0072] In general, performance of all carriers was relatively
similar. Overall, parent toner charge in both A-zone and J-zone was
equal or higher as the amount of residual CHMA was reduced as shown
in FIG. 3. A-zone blended toner charge was significantly increased
with lower residual CHMA as shown in FIG. 4. Blended toner in
J-zone had a more complicated dependence, but aside from the
highest amount of residual CHMA, also trended somewhat higher with
reduction in residual CHMA. RH ratios improved slightly for parent
toners as shown in FIG. 5, but were much better for blended toners
with reduced residual CHMA. In general, overall charge and RH
performance was clearly improved by reduced residual CHMA.
[0073] It will be appreciated that various of the above-disclosed
and other features and functions, or alternatives thereof, may be
desirably combined into many other different systems or
applications. Various presently unforeseen or unanticipated
alternatives, modifications, variations or improvements therein may
be subsequently made by those skilled in the art which are also
intended to be encompassed by the following claims.
* * * * *